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- W2013443023 abstract "Reactions of the linear triplatinum complex [Pt3(μ-dpmp)2(XylNC)2]2+ (3) with small organic molecules led to formation of asymmetrical A-frame triplatinum complexes with an additional bridge across one of the metal−metal bonds, where dpmp is bis((diphenylphosphino)methyl)phenylphosphine. Reaction of complex 3 with electron deficient alkynes (R1C⋮CR2: R1 = R2 = CO2Me; R1 = H, R2 = CO2Me; R1 = R2 = CO2Et) afforded a new series of triplatinum clusters formulated as [Pt3(μ-dpmp)2(μ-R1CCR2)(XylNC)2](PF6)2 (5a, R1 = R2 = CO2Me; 5b, R1 = H, R2 = CO2Me; 5c, R1 = R2 = CO2Et) in good yields. The complex cation of 5b was characterized by X-ray crystallography to have an asymmetrical A-frame structure comprising three Pt atoms bridged by two dpmp ligands, in which an acetylene molecule was inserted into one of the Pt−Pt bonds (triclinic, P1̄, a = 19.507(3) Å, b = 20.327(4) Å, c = 14.499(4) Å, α = 107.69(2)°, β = 102.08(2)°, γ = 71.30(1)°, V = 5148 Å3, Z = 2, R = 0.070, and Rw = 0.084). The Pt−Pt bond length is 2.718(1) Å and the Pt···Pt nonbonded distance is 3.582(1) Å. Treatment of 3 with an excess of HBF4·Et2O gave the asymmetrical cluster [Pt3(μ-dpmp)2(μ-H)(XylNC)2](BF4)3·CH2Cl2 (6·CH2Cl2), in 61% yield, and a similar reaction with p-NO2C6H4NC led to the formation of [Pt3(μ-dpmp)2(μ-R3NC)(XylNC)2](PF6)2·CH2Cl2 (7·CH2Cl2) in 94% yield (R3 = p-NO2C6H4). Complexes 6 and 7 are assumed to have a single atom-bridged, asymmetrical A-frame structures. Reaction of the complex syn-[Pt2(μ-dpmp)2(XylNC)2]2+ (1) with [MCl2(cod)] (M = Pt, Pd) gave the dimer−monomer combined trinuclear cluster [Pt2MCl2(μ-dpmp)2(XylNC)2](PF6)2 (8a, M = Pt, 89%; 8b, M = Pd, 55%). The structure of 8a was determined by X-ray crystallography to be comprised of a metal−metal-bonded diplatinum core and a monomeric platinum center bridged by two dpmp ligands with a face-to-face arrangement (triclinic, P1̄, a = 18.082(7) Å, b = 19.765(6) Å, c = 15.662(4) Å, α = 98.51(2)°, β = 94.24(3)°, γ = 109.82(2)°, V = 5161 Å3, Z = 2, R = 0.069, and Rw = 0.080). The Pt−Pt bond length is 2.681(2) Å and the Pt···Pt nonbonded distance is 3.219(2) Å. The heteronuclear complex 8b was transformed to an A-frame trinuclear cluster, [Pt2PdCl(μ-Cl)(μ-dpmp)2(XylNC)](PF6)2 (9), which was characterized by X-ray crystallography (monoclinic, C2/c, a = 33.750(9) Å, b = 28.289(9) Å, c = 23.845(8) Å, β = 118.19(4)°, V = 20066 Å3, Z = 8, R = 0.082, and Rw = 0.077). The diplatinum unit (Pt−Pt = 2.606(2) Å) is connected to the mononuclear Pd center by a chloride bridge (Pt···Pd = 3.103(3) Å, Pt−Cl−Pd = 79.6(3)°)." @default.
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- W2013443023 date "1996-01-01" @default.
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- W2013443023 title "Asymmetrical A-Frame Triplatinum Clusters Bridged by Small Organic Molecules and Bis((diphenylphosphino)methyl)phenylphosphine" @default.
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- W2013443023 doi "https://doi.org/10.1021/ic951186j" @default.
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